Supported catalysts

ABSTRACT

A supported catalyst comprising a support, an anchoring agent such as a heteropoly acid or anion, and a metal complex which is useful in a wide variety on organic reactions, especially the hydrogenation of substituted α,β unsaturated acids and esters, is provided. Various methods of preparing the supported catalyst of the present invention is also disclosed.

This patent research project was supported in part by a grant from theNational Science Foundation, Grant No. CTS-9312533.

RELATED APPLICATIONS

This application claims benefit of provisional application U.S. Ser. No.60/034,338, filed Dec. 23, 1996. This application is a divisional ofU.S. application Ser. No. 08/994,025, filed Dec. 18, 1997.

FIELD OF THE INVENTION

The present invention relates to a highly stable supported catalystwhich exhibits high reactivity and selectivity in a wide variety oforganic reactions. More specifically, the present invention relates to asupported catalyst which comprises a support, an anchoring agent and ametal complex, wherein the anchoring agent is a heteropoly acid, itslacunar or other crystalline or noncrystalline phases or their anions.Such a supported catalyst is particularly useful for, but not limitedto, the chiral hydrogenation of substituted α,β unsaturated acids oresters and α- or β-ketoesters or lactones. Various methods of preparingthe supported catalyst of the present invention are also providedherein.

BACKGROUND OF THE INVENTION

Catalytic processes using either homogeneous catalysts, i.e. thosepresent in the same phase as the reactant, or heterogeneous catalysts,i.e. those present as a separate phase in the reaction medium, haveplayed an important role in organic synthesis. Heterogeneous catalystsare insoluble; thus they can be readily separated from the reactionmixture and, generally, offer the potential for ready re-use. Despitethese advantages, prior art heterogeneous catalysts are rather limitedin the number and types of organic reactions in which they can be used.In addition, they are usually less selective than homogeneous catalystswhich are typically soluble metal salts or metal complexes. Indeed,homogeneous catalysts are not only more selective than heterogeneouscatalysts, but have been used to promote a wider variety of organicreactions. Nevertheless, difficulties can be encountered in separatingthe soluble, homogeneous catalyst, both the metal and the accompanyingligands, from the product. This not only presents problems with thepurity of the product, but also makes the re-use of the homogeneouscatalyst problematic. The potential loss of the ligand is particularlyserious in enantioselective reactions where chiral ligands are usuallyquite expensive.

Over the past twenty-five years, attempts have been made to"heterogenize" the more versatile homogeneous catalysts, the primary aimbeing to maintain reaction activity and selectivity of the homogeneousspecies while at the same time significantly increasing the ease ofseparation from the reaction medium. One such approach to achieve"heterogenization" involves reacting a metal complex or salt with asolid support such as a polymer or a metal oxide which had beenpreviously modified by the addition of phosphine or amine ligands to thesurface of the support. Catalysis Reviews, 16, 17-37 (1974) and ChemicalReviews, 81, 109 (1981) are reviews of the earlier literature concernedwith polymer supported complexes. Tetrahedron: Asymmetry, 6, 1109-1116(1995), Tetrahedron Letters, 37, 3375-3378 (1996) and ChemischeBerichte, 129 , 815-821 (1996) are examples of recent references in thisarea. From a practical approach, these catalysts are not widely usedsince their activities are frequently lower than those of thecorresponding homogeneous analogs. In addition, problems associated withpolymer swelling and attendant mass transport difficulties can beencountered, as well as the finding that activity is frequently lost onattempted re-use. Some success has been reported in preparing polymersupported chiral complexes, but the selectivity observed with the use ofsuch "heterogenized" species has generally been lower than that obtainedusing the homogeneous catalyst itself.

"Catalysis by Supported Complexes", Studies in Surface Science andCatalysis, Volume 8, Elsevier Publishing Company, Amsterdam, 1981 is anextensive review of the earlier work concerned with the anchoring ofmetal complexes onto surface modified oxides. Journal of Catalysis, 157,436-449 (1995) and Bulletin Societe de Chemie, France, 133, 351-357(1996) are some more recent references. While these materials do notmanifest significant swelling problems associated with the use ofpolymer supports, there are frequent reports of loss of activity onattempted re-use.

In rare instances, the oxide support does not have to be modified beforethe application of a metal complex. Journal of Molecular Catalysis, 8813-22 (1994) describes the interaction of Rh(OH) (CO) (PPh₃)₂ with analumina surface to give a supported catalyst for the hydrogenation ofalkenes and benzene. This report also states that the presence of theRh--OH entity is necessary for interaction with the surface of thealumina and that other complexes could not be attached to the oxidesurface.

Another problem associated with prior art catalysts made from metalcomplexes which are attached to either a modified polymer or metal oxidesurface is that their preparation techniques are rather specific and aredriven by the nature of the ligand to be attached. Hence, modificationof the catalyst to introduce another, more selective ligand is usuallyan arduous and complex task, if it is one that can be accomplished atall. This circumstance has particular importance where the preparationof enantioselective catalysts are concerned since optimal enantiomericexcess is usually obtained using a specific ligand or class of ligandsfor a given reaction or substrate.

Journal of Catalysis, 152, 25-30 (1995) describes the preparation ofchiral, supported aqueous-phase catalysts and their use in the,preparation of naproxen. These heterogeneous catalysts have the sameenantioselectivity as the homogeneous counterpart, but are 2 to 2.5times less active.

Heteropoly acids have long been used as solid acid catalysts and havebeen supported on various solid supports for use in this way. Forinstance, Chemistry Letters, 663 (1981) and Applied Catalysis 74,191-204 (1991) describe the use of heteropoly acids supported on carbonas solid acid catalysts, while Journal of Catalysis, 84, 402-409 (1983),Journal of Catalysis, 125 , 45-53 (1990) and Microporous Materials, 5,255-262 (1995) describe the use of silica as a support for heteropolyacids. Journal of Molecular Catalysis, 74, 23-33 (1992) describes thepillaring of anionic clays by heteropoly acids.

It has been known for some time that interaction of a heteropoly acidwith a metal salt can provide catalysts that are useful for a number ofdifferent oxidation and related reactions in which the redox propertiesof the heteropoly acid play an important role. For instance, U.S. Pat.No. 4,448,892 and Journal of Catalysis, 154, 175-186 (1995) describe theuse of such catalysts, where the same are prepared using a palladiumsalt, for the oxidation of alkenes to aldehydes or ketones. Similarcatalysts have also been used for the carbonylation of alkenes asdescribed in Jpn. Kokai Tokkyo Koho JP 62, 161,737 [Chemical Abstracts,108, 131037 (1988)]. The carbonylation of nitro aromatics is describedin Chemistry Letters, 795-796 (1990) and Jpn. Kokai Tokkyo Koho JP 03,93,765 [Chemical Abstracts, 115, 182846 (1991)] while alkane and alkeneoxidations are described in Chemical Communications, 1324-1325 (1989).

U.S. Pat. Nos. 5,116,796 and 5,250,739 as well as Inorganic Chemistry,34, 1413-1429 (1995) describe the formation of solubleiridium-heteropoly acid complexes which have been used to promote alkenehydrogenations and oxidations.

U.S. Pat. No. 4,590,298 describes the use of soluble rhodiumcyclopentadiene complexes in combination with heteropoly acids for thereaction of hydrogen and carbon monoxide with formaldehyde to give C₄-C₅ hydroxy ketones.

Chemistry Letters, 1595 (1985) describes the interaction of RhCl(PPh₃)₃with Li₄ SiMo₁₂ O₄₀ to give a soluble catalyst for the semihydrogenationof methyl phenyl acetylene.

U.S. Pat. No. 4,673,753 and Inorganic Chemistry, 29, 1667-1673 (1990)describe the combination of rhodium carbonyl phosphine complexes withheteropoly acids. The substances prepared are insoluble in toluene sothe catalytic reactions are run in this solvent to maintain aheterogeneous catalyst system. These species are used to catalyze theoxidation of CO by NO, the isomerization of 1-hexene and thehydroformylation of 1-hexene. There is no report on the re-use of thesecatalysts.

Despite the current state of the art, there is a continuing need todevelop stable heterogeneous catalysts which employ an active metalcomplex on an insoluble support, which catalysts are highly reactive andselective in organic reactions. Indeed, a particular need exists for thedevelopment of such catalysts which contain a chiral metal entitycapable of promoting an enantioselective reaction. The term "chiralmetal entity" is used herein to denote metal complexes which contain atleast one chiral ligand.

SUMMARY OF THE INVENTION

One aspect of the present invention relates to a supported catalystwhich comprises the following catalyst components: (i) a particulatesupport; e.g. an inorganic oxide or carbon; (ii) an "anchoring agent";and (iii) a metal complex. By "anchoring agent" is meant a heteropolyacid, its lacunar or other crystalline or non-crystalline phase materialor their anions. By "metal complex" is meant any catalytically activematerial which contains at least one transition metal atom or ion fromGroup IIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the Periodic Table ofElements to which one or more ligands are attached. The ligands can bespecies containing, for instance, phosphorous, nitrogen, oxygen, sulfur,halogen or atoms having an electron pair, as well as carbonyls, alkenesand dienes or other moieties which can coordinate with the transitionmetal atom or ion.

Another aspect of the present invention relates to a method of preparingthe aforementioned supported catalyst. In accordance with this aspect ofthe present invention, the supported catalyst is prepared by thefollowing steps:

(i) contacting a support with a heteropoly acid or anion underconditions effective to form a heteropoly acid or anion-containingsupport;

(ii) contacting a metal complex with said heteropoly acid oranion-containing support under conditions effective to form a supportedcatalyst;

(iii) activating the catalyst be either first use in the reactor or by areduction step such as a prehydrogenation; and

(iv) optionally, recovering said supported catalyst from.

In accordance with a second method of the present invention, thesupported catalyst is obtained by the following steps:

(i) contacting a heteropoly acid or anion with a metal complex underconditions effective to form a solution or suspension containing saidheteropoly acid or anion and said metal complex;

(ii) contacting a support with said solution or suspension prepared instep (i) under conditions effective to form a supported catalyst;

(iii) activating the catalyst be either first use in a reactor or by areduction step such as a prehydrogenation; and

(iv) optionally, recovering said supported catalyst from.

Another aspect of the present invention relates to a method of forming asupported catalyst which comprises the steps of:

(i) contacting a support with a heteropoly acid or anion underconditions effective to form a modified support comprising theheteropoly acid or anion;

(ii) contacting a catalytic precursor material with said supportproduced in step (i) under conditions effective to form a supportedcatalyst precursor;

(iii) contacting the supported catalyst precursor with a ligand underconditions effective to prepare a catalytically active supportedcatalyst;

(iv) activating the catalyst be either first use in a reactor or by areduction step such as prehydrogenation; and

(v) optionally, recovering said supported catalyst from.

In another aspect of the present invention, the supported catalyst canbe used to promote a wide variety of organic reactions which include,but are not limited to: hydrogenations, dehydrogenations,isomerizations, carbonylations, hydrogenolyses, hydroformylations,oxidations, carboxylations, aminations, silylations, carboalkoxylations,cyclopropanations, alkylations, allylations, arylations and othercarbon--carbon bond forming reactions. These reactions can be run ineither the vapor phase or in solution. Further, they can be run ineither a batch mode or in a continuous process.

Of particular importance is the use of the chiral supported catalyst ofthe present invention for the enantioselective hydrogenation ofprochiral compounds such as substituted α,β unsaturated acids or estersand α- or β-ketoesters or lactones.

A related process involves the use of the supported catalyst of thepresent invention to promote the hydroformylation of alkenes intoaldehydes and/or alcohols in the presence of CO and H₂ under conditionswhich are sufficient to convert said alkene into the correspondingaldehyde and/or alcohol.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a plot of the hydrogen uptake curves for the hydrogenation of2-acetamidocinnamic acid methyl ester using a Rh(Me-DUPHOS)(COD)catalyst supported on a phosphotungstic acid modified carbon supportprepared in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

As stated hereinabove, the present invention allows a homogeneouscatalyst to be supported with high activity, selectivity and stabilityin a wide variety of organic reactions. Specifically, the catalyst ofthe present invention comprises the following three components: aninsoluble support, an anchoring agent (a heteropoly acid, its lacunar orother crystalline or non-crystalline phases or their anions), and ametal complex. The supported catalyst of the present invention is stablein air while retaining or even surpassing the activity and selectivityof the corresponding homogeneous catalyst; but, being insoluble, it iseasily removed from the reaction mixture and is thus capable of extendedre-use. Moreover, the supported catalyst of the present invention quiteunexpectedly exhibits an increase in reactivity and selectivity afterre-use. Thus, the supported catalyst of the present invention is highlyuseful in a wide variety of applications including, but not limited to,pharmaceutical and agrochemical applications.

The support is a particulate amorphous or crystalline material having asufficient surface area to facilitate uniform distribution of theanchoring agent thereon. A particle size is selected to afford easyseparability from the reaction media, and may typically range from100-200 mesh.

The supported catalyst of the present invention can be made using any ofthe following methods. In the first method, a support is contacted witha heteropoly acid or anion under conditions which are effective to forma support which contains the heteropoly acid or anion.

Suitable supports include, but are not limited to: metal oxides such asalumina, silica, titania, zirconia, lanthana, zeolites and clays, aswell as carbon, resins, polymers and the like. The support may be usedas is, or it may be treated prior to use to remove unwanted specieswhich may adversely effect the activity of the catalyst. For example,the support may be calcined either in air or in an inert atmosphereprior to use.

The interaction between the anchoring agent and the support may beeffected by reaction as discussed below; but it is to be understood thatthe anchoring agent may be bonded to or intercalated by the supportsolely by physical and/or chemical attractive forces based upon van derWaals forces, donor/acceptor interactions and other surface phenomena.

Another method of treating the support involves the use of a modifierwhich has been found to increase the adhesion of the heteropoly acid oranion to the support. Suitable modifiers that may be employed in thepresent invention for this purpose include, but are not limited to:metal alkoxides such as titanium alkoxide, aluminum alkoxide, silanealkoxide, vanadium alkoxide and the like; polyisocyanates, hydroxyepoxides, cyano epoxides and other functionalized organic materials. Ofthe aforementioned modifiers, metal alkoxides are particularlypreferred.

When a modifier is employed in the present invention, the modifier iscontacted with the support in a solvent at a temperature of from about-25° to about 250° C. for a period of time of from about 1 min. to about50 hrs. The amount of modifier employed in the present invention variesdepending upon the type of support being employed. Typically, however,the modifier is present in about 0.01% to about 100% by weight of thesupport employed in the present invention.

As stated above, the support, either treated or nontreated, is thencontacted with a heteropoly acid or anion. The heteropoly acids employedin the present invention are conventional heteropoly acids well known tothose skilled in the art. The term "heteropoly acid" is used herein todenote any polyprotic mixed oxide which is generally composed of acentral ion or ions bonded to an appropriate number of oxygen atoms andsurrounded by a near spherical shell of octahedral oxometal speciesjoined together by shared oxygen atoms. The central atom or "heteroatom"is typically a cation having a ⁺ 3 to +5 oxidation state such as P⁺⁵ ,As⁺⁵, Si⁺⁴ or Mn⁺⁴. The metal species associated with the octahedra areusually Mo, W or V. The octahedra in the shell of the heteropoly acidcan be of uniform composition or contain different metal species.

As discussed in "Zeolites, Clays and Heteropoly Acids in OrganicSynthesis", Chapter 3, VCH Publishers, New York, 1992, suitableheteropoly acids include, but are not limited to: Keggin species such asphosphotungstic acid (PTA), phosphomolybdic acid (PMA), silicotungsticacid (STA) and the like; Dawson species; Waugh species; Andersonspecies; Silverton species; their lacunar and other crystalline ornon-crystalline forms; and anions of the preceding. When anions areused, the counterions can be, but are not limited to: alkali, alkaliearth or quaternary ammonium ions.

Contact of the support and the heteropoly acid or anion generally occursin a solvent at a temperature of from about -25° to about 250° C. for atime period of from about 1 min. to about 50 hrs. Preferably, thisoccurs at temperatures of between about 25° and about 75° C. for periodsof between 3 and 12 hours. Typically, in the present invention theheteropoly acid or its anion is present in a weight ratio with thesupport of from about 0.01:1 to about 20:1. This contact step may occurin air or it may be carried out in an inert atmosphere.

In accordance with the next step of the present invention, theheteropoly acid or anion-containing support is contacted with a metalcomplex under conditions which are effective to form a supportedcatalyst. By "metal complex" is meant any catalytically active materialwhich contains at least one transition metal atom or ion from GroupIIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the Periodic Table ofElements to which one or more ligands are attached. Suitable transitionmetal atoms or ions include: Sc, Y, Ti, Zr, Hf, V, Cr, Mo, W, Mn, Re,Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn and the like.Preferably, the metal complex will contain a metal atom or ion fromGroup VIII of the Periodic Table of Elements; e.g., Fe, Ru, Os, Co, Rh,Ir, Ni, Pd and Pt.

The ligands can be species containing, for instance, phosphorus,nitrogen, oxygen, sulfur, halogen or atoms having a free electron pair,as well as carbonyls, alkenes and dienes or other moieties which cancoordinate with the metal atom or ion. Suitable achiral ligands whichmay be employed in the present invention include, but are not limitedto: species such as cyclopentadiene, carbon monoxide, cyclooctadiene(COD) and tertiary phosphines. Suitable chiral ligands which may beemployed in the present invention include, but are not limited to:species such as (R,R) or (S,S)2,2'-bis(diphenylphosphino)1,1'-binaphthyl (BINAP),(2S,3S)-bis(diphenylphosphino)butane (CHIRAPHOS),2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane(DIOP), (R,R)-1,2-bis[(2-methoxyphenyl)phenylphosphino]ethane (DIPAMP),1,2-bis(2R,5R)-2,5-(dimethylphospholano)benzene (Me-DUPHOS) and (R)1,2-bis(diphenylphosphino)propane (PROPHOS). Mixtures of these ligandssuch as (COD) (Me-DUPHOS) are also contemplated herein. The use ofchiral ligands is particularly preferred in the present invention forpromoting enantioselective reactions.

Examples of metal complexes contemplated by the present inventioninclude, but are not limited to: Rh(COD) (DIPAMP)BF₄, Pd(R,R-BINAP)Cl₂,Rh(COD) (Me-DUPHOS)Cl and the like. In addition to metal complexes,other catalytically active compounds containing a Group VIII metal arealso contemplated herein. Examples of such catalytically activecompounds include, but are not limited to: the elemental Group VIIImetals, Group VIII metal salts, and the like.

The contacting step between the heteropoly acid or anion-containingsupport and the metal complex typically occurs in a solvent and at atemperature of from about -25° to about 250° C. for a time period offrom about 1 min. to about 50 hrs. Preferably this contacting takesplace at temperatures of between about 25° and about 50° C. for a timeperiod of between about 1 hr and about 3 hrs. Generally in the presentinvention, the metal complex is employed at a concentration such thatthe metal complex to heteropoly acid or anion molar ratio is from about0.1:1 to about 6:1; more preferably, from about 0.5:1 to about 1.5:1;and most preferably from about 0.75:1 to about 1:1.

The solvents employed in various steps of the present invention may bethe same or different, and are those which are capable of dissolving theanchoring agent and/or the metal complexes. A preferred solvent ismethanol, but other alcohols such as ethanol, propanol, hexanol,heptanol and the like, as well as water, ethers, esters, ketones andaliphatic or aromatic hydrocarbons, may also be employed in the presentinvention. The solvent may be employed as is, or it may be purified bytechniques well known in the art prior to its use. For example, thesolvent can be distilled and then passed over a bed or column containingan appropriate adsorbent material.

The solid supported catalyst of the present invention may then beactivated either by first use in a reactor or by a reduction step suchas a prehydrogenation.

The solid supported catalyst of the present invention may then beoptionally recovered using techniques well known to those skilled in theart. For example, the solid catalyst may be recovered by decantation,filtration or centrifugation. The recovered solid catalyst may be usedas is; or it may be washed with one of the aforementioned solvents priorto use to remove any anchoring agent or metal complex that is not boundto the support. The supported catalyst can then be dried.

In accordance with the second method of preparing the supported catalystof the present invention, the anchoring agent mentioned hereinabove iscontacted first with a metal complex to form a solution or suspensionand then that solution or suspension is contacted with a support.

The contact between the anchoring agent and the metal complex typicallyoccurs in a solvent at a temperature of from about -25° to about 250° C.for a period of time of from about 1 min. to about 50 hrs. Preferably,this contact takes place at temperatures of between about 25° to about60° C. for periods of time from about 15 min to about 1 hr. Generallythe metal complex is employed at a concentration such that the metalcomplex to anchoring agent molar ratio is from about 0.1:1 to about 6:1;more preferably, from about 0.5:1 to about 1.5:1; and most preferablyfrom about 0.75:1 to about 1:1.

The resulting solution or suspension containing the anchoring agent andthe metal complex may be used as is, or, in another embodiment of thepresent invention, the resulting solution or suspension is dried andthen slurried in a comparable solvent prior to contacting with the metalcomplex. The solvents employed in this embodiment of the presentinvention are the same as those previously mentioned hereinabove.

The solution or suspension containing the anchoring agent and metalcomplex is then contacted with one of the supports mentioned above. Thiscontact between the solution or suspension and the support generallyoccurs in a solvent at a temperature of from about -25° to about 250° C.for a period of time from about 1 min. to about 50 hrs. Preferably, thiscontacting takes place at a temperature of about 25° C. to about 60° C.for a period of time from about 3 hrs to about 12 hrs. In accordancewith this aspect of the present invention, the anchoring agent and metalcomplex solution or suspension is present in about 0.01% to about 150%by weight of the support employed in this contacting step. The thusformed supported catalyst is, optionally, recovered as previouslydescribed.

The activation by prehydrogenation can be accomplished by stirring thesupported catalyst under hydrogen typically at temperatures betweenambient and 50° C. and at pressures between 1 and 10 atm. for anappropriate amount of time to achieve activation.

In accordance with another aspect of the present invention, a supportedcatalyst is prepared by first contacting a support with an anchoringagent as described hereinabove. The support containing the anchoringagent is then contacted with a catalyst precursor material underconditions which are effective for forming a supported catalystprecursor.

By "catalyst precursor material" is meant any metal salt or complexwhich is used to prepare a catalytically active entity. Examples ofsuitable catalyst precursors include, but are not limited to, rhodiumcyclooctadiene dimer, ruthenium cyclooctadiene dimer, allyl palladiumdimer, rhodium chloride and the like.

The contacting of the anchoring agent-containing support and thecatalyst precursor typically occurs in a solvent at a temperature offrom about -25° to about 250° C. for a time period of from about 1 min.to about 50 hrs. Preferably this contacting takes place at temperaturesof between about 25° and about 50° C. for periods of between about 1 hrto about 3 hrs. Generally in the present invention, the catalystprecursor material is employed at a concentration such that theprecursor to anchoring agent molar ratio is from about 0.1:1 to about6:1; more preferably, from about 0.5:1 to about 1.5:1; and mostpreferably from about 0.75:1 to about 1:1. The catalyst supportedprecursor, optionally, may be washed and dried prior to treatment with aligand.

The thus formed catalyst supported precursor is then contacted with aligand which forms a catalytically active entity. It is noted that thecatalyst supported precursor itself may or may not be catalyticallyactive. It is, however, converted to a catalytically active entity bycontacting it with a suitable ligand. The ligands employed for thispurpose include those ligands mentioned hereinabove.

The concentration of the ligand which is added to the catalyst supportedprecursor is typically from about 1 to about 6 mmol per mmol of catalystprecursor material. The treatment of the catalyst supported precursorand the ligand typically occurs in a solvent at temperatures of fromabout -25° to about 250° C. for periods of from about 1 min to about 50hrs.

It should be mentioned that all of the above contacting steps may beconducted in air or they may be done in hydrogen or in an inert gasatmosphere, as appropriate. The activation by prehydrogenation iscarried out using the conditions mentioned hereinabove.

The above description illustrates the methods which can be used informing the supported catalyst of the present invention. It isemphasized that all three catalyst components of the present invention,i.e. the support, the anchoring agent, and the metal complex are neededfor optimum catalytic activity, stability and selectivity. Catalysts notcontaining all three catalyst components of the present inventionexhibit inferior results. For example, while catalysts prepared withoutthe presence of the anchoring agent may sometimes show activity, thestability and activity in all cases is significantly lower than that ofthe supported catalyst of the present invention. In an appropriatesolvent the heteropoly acid-metal complex product without the supportmay appear to be insoluble. While this material may be used as aheterogeneous catalyst a portion of the catalytically active speciesdoes dissolve resulting in a loss of catalyst.

The supported catalyst of the present invention imparts improvedcatalytic properties such as catalytic activity, stability andselectivity as compared to the corresponding homogeneous catalyst or asto catalytic species prepared only from a heteropoly acid and a metalcomplex. Moreover, the supported catalyst of the present inventionadvantageously and unexpectedly exhibits an increase in catalyticactivity and selectivity when the catalyst is re-used. Without wishingto be bound by any theory it is thought that the observed increase inactivity and selectivity when compared to the soluble species is theresult of changes in the steric environment of the active metal in thesupported moiety. Increases in stability may be brought about by thepresence of the anchoring agent.

The catalyst itself comprises a relatively uniform distribution ofactive catalytic sites formed about the supporting particles, but remotetherefrom to the extent of the selected anchoring agent bridge. Thisshell of active sites may typically be present at a distance, forexample, 10-14 Å from the support particle itself, thereby affordingexcellent accessibility to reactants.

A further advantage of the supported catalyst of the present inventionis that it is insoluble; and leaching of the metal, which is common withprior art supported homogeneous catalysts, is not observed.

In view of the above advantages, the supported catalyst of the presentinvention can be used to promote a wide variety of organic reactionswhich include, but are not limited to: hydrogenations, dehydrogenations,isomerizations, carbonylations, hydrogenolyses, hydroformylations,oxidations, carboxylations, aminations, silylations, carboalkoxylations,cyclopropanations, alkylations, allylations, arylations and othercarbon--carbon bond forming reactions. These reactions can be run ineither the vapor phase or in solution. Further, they can be run ineither a batch mode or in a continuous process using conditions wellknown to those skilled in the art.

In a highly preferred embodiment of the present invention, the supportedcatalyst of the present invention is employed in hydrogenatingsubstituted α,β unsaturated acids or esters or other prochiralsubstrates. In accordance with this aspect of the present invention, asubstituted α,β unsaturated acid or ester having the formula ##STR1##wherein R¹, R² and R³ are the same or different and are hydrogen, alkylcontaining from 1 to about 35 carbon atoms, alkenyl containing from 1 toabout 35 carbon atoms, alkynyl containing from 1 to about 35 carbonatoms, aryl containing from about 6 to about 18 carbon atoms, amine,amide, or alkoxide containing from about 1 to about 35 carbon atoms, andR is hydrogen or alkyl having from about 1 to about 35 carbon atoms, iscontacted with a supported catalyst of the present invention in thepresence of H₂ under conditions which are effective to selectivelyhydrogenate the substituted α,β unsaturated acid or ester into a desiredproduct. It is noted that the above substituents may be straight orbranched as well as being unsubstituted or substituted with one of thesubstituents mentioned hereinabove. The aryl substituents may also bebicyclic or fused species.

Of particular interest is the enantioselective hydrogenation of thosecompounds in which R³ is not hydrogen or R¹ is different from R² andneither is hydrogen. Hydrogenation of these prochiral substrates over achiral supported catalyst of the present invention leads to theselective formation of one of the enantiomers of the product.

Preferred substituted α,β unsaturated acids or esters contemplated bythe present invention include, but are not limited to:2-acetamidocinnamic acid methyl ester, 2-acetamidocinnamic acid,2-acetamidoacrylic acid methyl ester, 2-acetamidoacrylic acid,dimethylitaconate, itaconic acid, 2-methylpentenoic acid,2-methylhexenoic acid, and 2-(6-methoxy-2-naphthyl)acrylic acid.

In another preferred embodiment of the present invention, the supportedcatalyst of the present invention is employed in hydrogenating carbonylgroups, particularly prochiral ketones, α-ketoesters, α-ketolactones orβ-ketoesters.

The hydrogenation conditions employed in the present invention are thosethat are typically employed in the prior art for carrying out such areaction.

In yet another preferred embodiment of the present invention, a processfor hydroformylating alkenes into their corresponding aldehydes and/oralcohols is provided. In accordance with this aspect of the presentinvention, an alkene containing from 2 to about 35 carbon atoms iscontacted with a supported catalyst of the present invention in thepresence of H₂ and CO and under conditions effective to convert thealkene to the desired product. The hydroformylation reaction may becarried out in the gas phase or in the liquid phase using conditionswell known to those skilled in the art.

The following examples are given to illustrate the scope of the presentinvention. Because these examples are given for illustrative purposesonly, the invention embodied herein should not be limited thereto.

EXAMPLE I

This example illustrates a procedure for the preparation of a supportedcatalyst prepared in accordance with the method of the present inventiondescribed above.

Four grams of the support material was suspended in 30 mL of methanoland stirred for 15 minutes after which time a solution of 200 micromolesof the heteropoly acid in 25 mL of methanol was added over a short time.The resulting mixture was stirred at room temperature for 60 minutes. Asolution of 200 micromoles of the metal complex catalyst in 10 mL ofmethanol was then added slowly under vigorous stirring. After theaddition was completed, stirring at room temperature was continued forabout eight to about twelve hours after which time the suspension wastransferred to a centrifuge tube and the solid separated bycentrifugation. After decantation of the supernatant liquid, the solidwas washed several times with methanol until no color was observed inthe wash liquid. The residue was dried under vacuum and stored in ascrew capped vial until use.

EXAMPLE II

This example illustrates a second procedure for the preparation of asupported catalyst prepared in accordance with the method of the presentinvention described above.

To a catalytic reactor was added 10 mL of methanol and 100 mg of thesupport material. After stirring for 15 minutes in air, a solution of 20micromoles of the heteropoly acid in 2.5 mL of methanol was added andthe suspension stirred for 30 minutes at room temperature. To thismixture was slowly added 1 mL of methanol containing 20 micromoles ofthe metal complex catalyst and the suspension stirred at roomtemperature for several hours in air and the stirring stopped. After thecatalyst had settled, the liquid was withdrawn with a syringe and a 15mL portion of methanol was added to the reactor. The mixture was stirredagain for about 30-45 minutes, and the liquid again withdrawn. Thiswashing procedure was repeated at least three times or until no colorwas observed in the wash liquid. After this, the air in the reactor wasreplaced with hydrogen, a solution of the reaction substrate wasintroduced into the reactor and the reaction initiated.

EXAMPLE III

This example illustrates a third procedure for the preparation of asupported catalyst in accordance with the method of the presentinvention.

To a catalytic reactor was added 10 mL of methanol and 300 mg of thesupport material. The reactor was filled with an inert gas and sealedwith all further additions made through a septum adapter. After stirringfor 15 minutes, a solution of 20 micromoles of the heteropoly acid in2.5 mL of methanol was added and the suspension stirred for 30 minutesat room temperature. To this mixture was slowly added 1 mL of methanolcontaining 20 micromoles of the metal complex catalyst and thesuspension stirred for several hours at room temperature and thestirring stopped. After the catalyst had settled, the liquid waswithdrawn with a syringe and a 15 mL portion of methanol was added tothe reactor. The mixture was stirred again for about 30 to 45 minutes,and the liquid again withdrawn. This washing procedure was repeated atleast three times or until no color was observed in the wash liquid.After this, the inert gas in the reactor was replaced with hydrogen, asolution of the reaction substrate was introduced into the reactor andthe hydrogenation initiated.

EXAMPLE IV

This example illustrates a fourth procedure for the preparation of asupported catalyst of the present invention.

To a suspension of 1 gram of Norit carbon in 10 mL of methanol was addeda solution of 200 micromoles of the heteropoly acid in 25 mL of methanolat a rate of 1 mL/min. After this addition was complete, a solution of400 micromoles of a base such as NaOH in 15 mL of methanol was added atthe same rate and the resulting suspension was stirred at roomtemperature for an additional 12 hours. The suspension was centrifugedand the supernatant decanted. The modified support was washed with 20 mLportions of methanol until all of the soluble material had been removed.The solid was then dried under vacuum and stored in a glass vial untiluse. To a 180 mg portion of the modified support suspended in 3 mL ofmethyl acetate was added, with stirring, a solution of 25 micromoles ofPd(R,R-BINAP)Cl₂ in 3 mL of methylene chloride. The mixture was stirredat room temperature for about 12 hours, washed five times with 5 mLportions of methyl acetate and then used for an appropriate reaction.The supported catalyst can also be dried and stored for future use.

EXAMPLE V

This example describes the general procedure used for the hydrogenationof the various substrates over the catalysts prepared as described inthe previous examples.

To a 25 mL reaction flask was added an amount of catalyst prepared byone of the procedures described in Examples I-III and containing 20micromoles of the active metal complex. A solution of 0.82 millimoles ofthe reaction substrate in 10 mL of solvent was then added and the flaskwas evacuated and filled with hydrogen three times. The temperature andpressure in this reactor were set to the appropriate values and thereactor was stirred at such a rate as to avoid mass transfer control ofthe reaction to initiate the reaction. The amount of hydrogen taken upwas measured by a computerized system for introducing into the reactorpulses containing known quantities of hydrogen. These pulses wereintroduced is into the reactor at such a rate as to maintain essentiallya constant pressure of hydrogen in the reactor system with the time ofeach pulse also recorded by the computer. After hydrogen absorptionceased the catalyst was separated from the reaction solution and theproduct was analyzed by gas chromatography or HPLC using an appropriatecolumn.

The results of some of these hydrogenations run using catalysts preparedusing the procedures described in Examples I, II and III are listed inTables 1 through 4.

EXAMPLE VI

This example illustrates the hydrogenation of 2-acetamidoacrylic acidmethyl ester over a Rh(DIPAMP)/PTA/Montmorillonite Clay catalystprepared using the procedure described in Example I whereMoritmorillonite clay was used as the support material, phosphotungsticacid (PTA) was the heteropoly acid and Rh(COD) (DIPAMP)BF₄ was the metalcomplex catalyst.

A 25 mL reaction flask was placed 400 mg of the catalyst,Rh(DIPAMP)/PTA/Montmorillonite clay, prepared following the proceduredescribed in Example I where Montmorillonite clay was used as thesupport material, phosphotungstic acid (PTA) was the heteropoly acid andRh(COD)(DIPAMP)BF₄ was the metal complex catalyst. A solution of 1.26millimoles of 2-acetamidoacrylic acid methyl ester in 10 mL of methanolwas then added and the flask was evacuated and filled with hydrogenthree times and the reaction initiated at atmospheric pressure and roomtemperature with computer monitoring of the hydrogen uptake. Afterhydrogen absorption ceased the product was analyzed by gaschromatography using a β-cyclodextrin Chiraldex column. As listed inTable 1 the hydrogen uptake occurred at a rate of 0.11 moles H₂ /moleRh/min with the product having an enantiomeric excess (ee) of 92%. Aftermultiple re-use the catalyst had an activity of 0.80 moles H₂ /moleRh/min and the product had an ee of 92%. The activity and selectivity ofthis catalyst was retained after storage for at least eight months atroom temperature in a screw capped vial in air as illustrated by thedata given in Table 1.

EXAMPLE VII

This example illustrates the hydrogenation of 2-acetamidoacrylic acidmethyl ester over a Rh(DIPAMP)/PTA/Montmorillonite clay catalystprepared using the procedure described in Example III whereMontmorillonite clay was used as the support material, phosphotungsticacid (PTA) was the heteropoly acid and Rh(COD) (DIPAMP)BF₄ was the metalcomplex catalyst.

A 25 mL reaction flask contained the catalyst prepared in a Heatmosphere from 400 mg of Montmorillonite K, 20 micromoles ofphosphotungstic acid (PTA) and 20 micromoles of the Rh(COD) (DIPAMP)BF₄complex following the procedure described in Example III. A solution of1.26 millimoles of 2-acetamidoacrylic acid methyl ester in 10 mL ofmethanol was then added and the flask was evacuated and filled withhydrogen three times and the reaction initiated at atmospheric pressureand room temperature with computer monitoring of the hydrogen uptake.After hydrogen absorption ceased, the product was analyzed by gaschromatography using a β-cyclodextrin Chiraldex column. As listed inTable 2, the hydrogen uptake occurred at a rate of 0.18 moles H₂ /moleRh/min with the product having an enantiomeric excess (ee) of 76%. Aftermultiple re-use the catalyst had an activity of 0.56 moles H₂ /moleRh/min and the product had an ee of 91%.

EXAMPLE VIII

This example illustrates the hydrogenation of methyl 2-acetamidoacrylicacid methyl ester over a Rh(DIPAMP)/PTA/Al₂ O₃ catalyst prepared usingthe procedure described in Example III where gamma alumina was used asthe support material, phosphotungstic acid (PTA) was the heteropoly acidand Rh(COD)(DIPAMP)BF₄ was the metal complex catalyst.

A 25 mL reaction flask contained the catalyst prepared in a Heatmosphere from 300 mg of gamma alumina, 20 micromoles ofphosphotungstic acid (PTA) and 20 micromoles of the Rh(COD) (DIPAMP)BF₄complex following the procedure described in Example III. A solution of1.26 millimoles of 2-acetamidoacrylic acid methyl ester in 10 mL ofmethanol was then added and the flask was evacuated and filled withhydrogen three times and the reaction initiated at atmospheric pressureand room temperature with computer monitoring of the hydrogen uptake.After hydrogen absorption ceased the product was analyzed by gaschromatography using a β-cyclodextrin Chiraldex column. As listed inTable 2, the hydrogen uptake occurred at a rate of 0.32 moles H₂ /moleRh/min with the product having an enantiomeric excess (ee) of 90%. Aftermultiple re-use the catalyst had an activity of 1.67 moles H₂ /moleRh/min and the product had an ee of 92%.

EXAMPLE IX

In this example, a Rh(COD) (DIPAMP)BF₄ catalyst was supported on varioussupports which were previously treated with phosphotungstic acid and thesupported catalysts were used in the hydrogenation of 2-acetamidoacrylicacid methyl ester. The supported catalysts of this example were preparedusing the procedure described in Example III using Montmorillonite Kclay, carbon, aluminum and lanthana as the support materials.

The results of this experiment are shown in Table 2. Specifically, thedata in Table 2 illustrate that the supported catalysts of the presentinvention exhibited high activity and selectivity after one use.Moreover, an unexpected increase in activity and selectivity wasobserved after the first use.

EXAMPLE X

In this example, a supported catalyst of the present invention wasprepared using the procedure described in Example III using differentheteropoly acids, i.e. phosphotungstic, silicotungstic andsilicomolybdic. The support in each instance was Montmorillonite K clayand the metal complex was Rh(COD) (DIPAMP)BF₄. The supported catalystsprepared in this example were used in the hydrogenation of2-acetamidoacrylic acid methyl ester.

The results of using different heteropoly acids in the preparation ofthe supported catalysts of the present invention are shown in Table 3.Again, the supported catalysts of this example showed good activity andselectivity after one use. An increase in activity and selectivity wasunexpectedly observed after the first use.

EXAMPLE XI

In this example, a comparison between various homogeneous catalysts,namely Rh(DIPAMP), Rh(PROPHOS) and Rh(Me-DUPHOS), and the correspondingsupported catalysts prepared in accordance with the present inventionwere made for the hydrogenation of 2-acetamidoacrylic acid methyl ester.The supported catalysts were prepared using the procedure described inExample III using gamma alumina as the support material andphosphotungstic acid (PTA) as the heteropoly acid and Rh(COD)(DIPAMP)BF₄, Rh(COD) (Me-DUPHOS)Cl and Rh(COD)(Me-DUPHOS)Cl,respectively, as the metal complex catalysts. The results of this studyare shown in Table 4. Specifically, the data in Table 4 illustrate thatthe supported catalysts of the present invention exhibit efficientactivity and selectivity when compared to their soluble homogeneouscounterparts.

Moreover, the supported catalysts of the present invention unexpectedlyexhibited an increase in activity and selectivity during re-use.

EXAMPLE XII

This example illustrates the hydrogenation of 2-acetamidocinnamic acidmethyl ester over a Rh(Me-DUPHOS)/PTA/Carbon catalyst prepared using theprocedure described in Example III where carbon was used as the supportmaterial, phosphotungstic acid (PTA) was the heteropoly acid andRh(COD)(Me-DUPHOS)Cl was the metal complex catalyst.

A 25 mL reaction flask contained the catalyst prepared in a Heatmosphere from 100 mg of carbon, 20 micromoles of phosphotungstic acid(PTA), 40 micromoles of NaOH and 20 micromoles of theRh(COD)(Me-DUPHOS)Cl complex following the procedure described inExample III. A solution of 0.82 millimoles of 2-acetamidocinnamic acidmethyl ester in 10 mL of methanol was then added and the flask wasevacuated and filled with hydrogen three times and the reactioninitiated at atmospheric pressure and room temperature with computermonitoring of the hydrogen uptake. After hydrogen absorption ceased theproduct was analyzed by gas chromatography using a β-cyclodextrinChiraldex column. The hydrogen uptake occurred at a rate of 0.18 molesH₂ /mole Rh/min with the product having an enantiomeric excess (ee) of93%. After multiple re-use the catalyst had an activity of 0.97 moles H₂/mole Rh/min and the product had an ee of 94%.

EXAMPLE XIII

In this example, a Rh(Me-DUPHOS)(COD) BF₄ catalyst supported on aphosphotungstic acid modified carbon support prepared in accordance withExample III was used in the hydrogenation of 2-acetamidocinnamic acidmethyl ester. The hydrogenation reactions were run at atmosphericpressure and at 25° C. The catalyst was re-used and the filtrate afterthe first hydrogenation showed no activity showing that there was nosoluble catalyst present in the liquid.

The results of this experiment are shown in FIG. 1. Specifically, theactivity of the catalyst increased after the first use.

EXAMPLE XIV

This example illustrates the hydrogenation of dimethylitaconate over aRu(S,S-BINAP)/PTA/SuperFlow clay catalyst prepared using the proceduredescribed in Example III where SuperFlow clay was used as the supportmaterial, phosphotungstic acid (PTA) was the heteropoly acid andRu(SS-BINAP) (NEt₃)Cl₂ was the metal complex catalyst.

A 25 mL reaction flask contained the catalyst prepared in a Heatmosphere from 200 mg of Clarion 470 SuperFlow clay, 10 micromoles ofphosphotungstic acid (PTA) and 10 micromoles of theRu(SS-BINAP)(NEt₃)Cl₂ complex following the procedure described inExample III. A solution of 1.42 millimoles of dimethylitaconate in 8 mLof methanol was then added and the flask was evacuated and filled withhydrogen three times and the reaction initiated at atmospheric pressureand room temperature with computer monitoring of the hydrogen uptake.After hydrogen absorption ceased the product was analyzed by gaschromatography using a β-cyclodextrin Chiraldex column. The hydrogenuptake occurred at a rate of 0.06 moles H₂ /mole Ru/min with the producthaving an enantiomeric excess (ee) of 81%. After multiple reuse thecatalyst had an activity of 0.09 moles H₂ /mole Ru/min and the producthad an ee of 91%.

EXAMPLE XV

This example illustrates the hydroformylation of 1-hexene over a Rh(P(C₆H₅)₃)₃ Cl/PTA/Montmorillonite clay catalyst prepared using the proceduredescribed in Example III where montmorillonite clay was used as thesupport material, phosphotungstic acid (PTA) was the heteropoly acid andRh(P(C₆ H₅)₃)₃ Cl was the metal complex catalyst.

The modified support was prepared from a suspension of 1.5 g ofMontmorillonite K in 10 mL of methanol and 120 micromoles of PTA in 5 mLof methanol. The catalyst was prepared from this support and 5 mL oftoluene containing 100 micromoles of Rh(P(C₆ H₅)₃)₃ Cl. The resultingsuspension was stirred at 70° C. overnight and the catalyst washed with20 mL portions of toluene at least three times or until all of thesoluble rhodium complex had been removed using the procedure describedin Example III. To a 200 mg portion of this catalyst in a stainlesssteel autoclave was added 30 mL of toluene and 6 mL of 1-heptene. Theautoclave was flushed three times with a 1:1 mixture of CO and H₂,pressurized to 1000 psig, the temperature was raised to 80° C. andstirring initiated at 800 rpm. The reaction was run for 24 hours afterwhich time the liquid was removed and a second portion of 1-heptene andtoluene were injected into the autoclave and the hydroformylation runagain. This procedure was repeated three times with the productsanalyzed by GC-MS using a 30 m×0.25 mm HP-1 capillary column. Thereaction data is listed in Table 5 along with corresponding data for thereaction run using a soluble Rh(P(C₆ H₅)₃)₃ Cl catalyst.

The isomerization product was 2-heptene (1) and the hydroformylationproducts were 1-octanal (2), 2-formylheptane (3) and 3-formylheptane(4). The foregoing numbers are utilized to identify the specificproducts in Table 5.

EXAMPLE XVI

This example illustrates the allylation of sodium dimethylmalonate by2-butenyl acetate over a Pd(R,R-BINAP)/PTA/Carbon catalyst preparedusing the procedure described in Example IV.

To the catalyst described in Example IV was added a solution of 160 mgof sodium dimethylmalonate in 5 mL of tetrahydrofuran and the suspensionstirred for 10 minutes. 2-Butenyl acetate (60 microliters) was thenadded by syringe and the reaction mixture stirred at room temperaturefor 12 hours. The reaction liquid was then removed and analyzed by gaschromatography. The reaction data are listed in Table 6 along with dataobtained on running the reaction using a soluble Pd(R,R-BINAP)Cl₂catalyst.

The products were trans methyl (2-carbomethoxy)-4-hexenoate (5), cismethyl (2-carbomethoxy)-4-hexenoate (6) and (R) and (S) methyl(2-carbomethoxy-3-methyl)-4-pentenoate (7). The foregoing numbers areutilized to identify the specific products in Table 6.

EXAMPLE XVII

The example illustrates the preparation of a titanium alkoxide modifiedsilica and its use as a support for Rh(P(C₆ H₅)₃)₃ Cl/PTA.

To a flask containing 100 mL of dry toluene was added 30 g of ICN60silica which had been previously dried by heating at 90° C. for one hourunder a vacuum of 18 mm Hg immediately before use. To this suspensionwas added in one portion a solution of 7.65 g of titanium isopropoxidein 30 mL of dry toluene and the flask was purged with nitrogen. Thetemperature of the suspension was slowly raised to 95°-100° C. and kept,with stirring, at that temperature overnight. After cooling, the solidwas washed three times with 100 mL portions of dry toluene and two timeswith freshly distilled methanol.

To this solid was added 50 mL of dry methanol and a solution of 12.9 gof phosphotungstic acid in methanol. The suspension was stirredovernight at room temperature under dry nitrogen and the solid separatedand washed five times with 100 mL portions of methanol. The solid wasdried at 60° for one hour.

To 400 mg of this modified support in 10 mL of acetone was added asolution of 20 micromoles of Rh(P(C₆ H₅)₃)₃ Cl in 2 mL of acetone afterpurging the flask with nitrogen. The resulting slurry was stirred atroom temperature under nitrogen for 2 hours and the liquid extractedfrom the reactor. The solid was washed with 10 mL portions of acetoneuntil there was no color in the wash liquid. The catalyst was driedunder vacuum at room temperature for two hours and then used for thehydrogenation of 1-hexene using the procedure described in Example V.After each use the colorless liquid was removed from the reactor andfresh solvent and reactant were added for an additional hydrogenation.This catalyst was re-used eight times with no loss of activity nor anyloss of the metal complex.

EXAMPLE XVIII

This example illustrates the use of this technique for the supporting ofa non-precious metal complex. The support used is a titanium alkoxidemodified silica.

One gram of the titanium alkoxide modified silica support with theattached PTA as described in Example XVII and 10 mL of tetrahydrofuran(THF) were placed in a flask. After purging the flask with nitrogen,65.4 mg of NiCl₂ (TPP)₂ dissolved in 1 mL of THF was added and theresulting slurry was stirred at room temperature for 2 hours(TPP=triphenylphosphine). The liquid was extracted and the solid washed5 times with 20 mL portions of dry THF. The catalyst was dried undervacuum at room temperature for two hours and used immediately.

To 500 mg of this catalyst was added 6 mL of THF and 1.62 mL of a coldsolution containing 2.9 mmole of phenyl lithium. The mixture was cooledto 0° C. under stirring and 0.42 mL of B(OCH₃)₃ (3.62 mmol) was slowlyadded followed by 0.167 ml (1.44 mmole) of allyl methyl carbonate andthe temperature was allowed to rise to ambient. The mixture was thenheated, with stirring, at 60° C. for 12 hours. The liquid was separatedfrom the solid catalyst and poured into a mixture of 20 mL of pentaneand 20 mL of saturated ammonium chloride solution. After vigorousshaking the organic layer was separated and filtered through a Celitepad. After drying and evaporation of the organic phase, gaschromatographic analysis of the residue using an HP-1 column showed that3-phenylpropene-1was formed in a yield identical to that obtained usingthe soluble nickel catalyst.

While the invention has been particularly shown and described withrespect to preferred embodiments thereof, it will be understood by thoseskilled in the art that the foregoing and other changes in form anddetail may be made without departing from the spirit and scope of theinvention.

                  TABLE 1.sup.a                                                   ______________________________________                                        Support      Use #       Rate.sup.b                                                                           ee                                            ______________________________________                                        Montmorillonite                                                                            1           0.11   92%                                             K clay 3 0.80 92%                                                              .sup. 1.sup.c 0.18 92%                                                        .sup. 3.sup.c 0.54 94%                                                       Carbon 1 0.07 75%                                                              3 0.50 78%                                                                 ______________________________________                                         .sup.a Examples of data obtained on hydrogenation of 2acetamidoacrylic        acid methyl ester over supported Rh(DIPAMP)/PTA catalysts supported on        Montmorillonite clay and carbon prepared using the procedure described in     Example I.                                                                    .sup.b moles H.sub.2 /mole Rh/min                                             .sup.c Data obtained using a catalyst which had been stored in air for        about eight months.                                                      

                  TABLE 2.sup.a                                                   ______________________________________                                        Support       Use #       Rate.sup.a                                                                           ee                                           ______________________________________                                        Montmorillonite K                                                                           1           0.18   76%                                             3 0.56 91%                                                                   Carbon 1 0.07 83%                                                              3 0.40 90%                                                                   Alumina 1 0.32 90%                                                             3 1.67 92%                                                                   Lanthana 1 0.38 91%                                                            3 0.44 92%                                                                 ______________________________________                                         .sup.a Examples of data obtained on hydrogenation of 2acetamidoacrylic        acid methyl ester over supported Rh(DIPAMP)/PTA catalysts supported on        different supports prepared using the procedure described in Example III.     .sup.b moles H.sub.2 /mole Rh/min                                        

                  TABLE 3.sup.a                                                   ______________________________________                                        Heteropoly Acid                                                                            Use #       Rate.sup.b                                                                           ee                                            ______________________________________                                        Phosphotungstic                                                                            1           0.18   76%                                              3 0.56 91%                                                                   Silicotungstic 1 0.04 55%                                                      3 0.31 87%                                                                   Silicomolybdic 1 0.23 92%                                                      3 1.13 94%                                                                 ______________________________________                                         .sup.a Examples of data obtained on hydrogenation of 2acetamidoacrylic        acid methyl ester over supported Rh(DIPAMP)/heteropoly acid catalysts         supported on Montmorillonite K clay with different heteropoly acids           prepared using the procedure described in Example III.                        .sup.b moles H.sub.2 /mole Rh/min                                        

                  TABLE 4.sup.a                                                   ______________________________________                                                        Supported.sup.b                                                                             Soluble.sup.c                                   Catalyst     Use #    Rate.sup.d                                                                           ee     Rate.sup.d                                                                         ee                                   ______________________________________                                        Rh(DIPAMP)   1        0.32   90%    0.25 76%                                     3 1.67 92% na na                                                             Rh(PROPHOS) 1 2.0 68% 0.26 66%                                                 3 2.6 63% na na                                                              Rh(Me-DUPHOS) 1 1.8 83% 3.3  96%                                               3 4.4 95% na na                                                            ______________________________________                                         .sup.a Examples of data obtained on hydrogenation of 2acetamidoacrylic        acid methyl ester over different rhodium complexes heteropoly acid            catalysts supported on gamma alumina which had been treated with              phosphotungstic acid using the procedure described in Example III.            .sup.b Alumina/PTA supported metal catalysts.                                 .sup.c Unsupported metal catalysts in solution.                               .sup.d moles H.sub.2 /mole Rh/min                                        

                  TABLE 5.sup.a                                                   ______________________________________                                                    Isomerization                                                                            Hydroformylation                                       Catalyst % Conv.  %1           %2  %3   %4  2/3                               ______________________________________                                        Soluble.sup.b                                                                          90       --           48  38   9   1.3                                 Supported.sup.c 78 15 49 29 -- 1.7                                            (1st use)                                                                     (2nd use) 65 12 40 24 -- 1.6                                                  (3rd use) 70 10 44 25 -- 1.8                                                ______________________________________                                         .sup.a Examples of data obtained on hydroformylation of 1heptene over a       Rh(P(C.sub.6 H.sub.5).sub.3).sub.3 Cl/PTA/Montmorillonite clay catalyst       prepared using the procedure described in Example III with the reaction       run using the procedure described in Example XV. The compound identities      are listed in Example XV                                                      .sup.b Unsupported metal catalyst in solution.                                .sup.c Montmorillonite/PTA supported metal catalyst.                     

                  TABLE 6.sup.a                                                   ______________________________________                                                Rxn                                                                     Catalyst Time Conv. %5 %6 %7 ee % 5/6 5 + 6/7                               ______________________________________                                        Soluble.sup.b                                                                         24 hr   96%     56  6   38  26    9.3  1.6                              Supported.sup.c 12 hr 100% 76 1.5 22 27 50 3.5                                (First Use)                                                                   Second Use 12 hr 100% 78 1.2 21 31 65 3.8                                     Fourth Use 12 hr 100% 78 1 21 30 78 3.9                                     ______________________________________                                         .sup.a Examples of data obtained on allylation of sodium dimethylmalonate     by 2butenyl acetate over a Pd(R,RBINAP)/PTA/Carbon catalyst prepared usin     the procedure described in Example IV with the reaction run using the         procedure described in Example XVI. The compound identities are listed in     Example XVI                                                                   .sup.b Unsupported metal catalyst in solution.                                .sup.c Carbon/PTA supported metal catalyst.                              

What is claimed is:
 1. A process for the hydrogenation of a substitutedα,β unsaturated acid or ester, said process comprising contacting asubstituted α,β unsaturated acid or ester of the formula: ##STR2##wherein R¹, R² and R³ are the same or different and are hydrogen, alkylcontaining from 1 to about 35 carbon atoms, alkenyl containing from 1 toabout 35 carbon atoms, alkynyl containing from 1 to about 35 carbonatoms, aryl containing about 6 to about 18 carbon atoms, amine, amide,or alkoxide containing from 1 to about 35 carbons atoms; and R ishydrogen or alkyl containing from 1 to about 35 carbon atoms with asupported catalyst comprising a support, an anchoring agent, and a metalcomplex, wherein said anchoring agent is a heteropoly acid, its lacunaror other crystalline or non-crystalline phase or the respective anionand wherein said anchoring agent forms a bridge between the support andthe metal complex by direct interaction with the metal of said metalcomplex in H₂ under conditions effective to selectively hydrogenate thesubstituted α,β unsaturated acid or ester into a desired product.
 2. Theprocess of claim 1 wherein said substituted α,β unsaturated acid orester is 2-acetamidocinnamic acid methyl ester, 2-acetamidocinnamicacid, 2-acetamido acrylic acid methyl ester, 2-acetamido acrylic acid,dimethylitaconate, itaconic acid, 2-methylpentenoic acid,2-methylhexenoic acid or 2-(6-methoxy-2-naphthyl)acrylic acid.
 3. Theprocess of claim 2 wherein said substituted α,β unsaturated acid orester is a prochiral substituted α,β unsaturated acid or ester and saidcatalyst is a chiral catalyst.
 4. The process of claim 2 wherein saidhydrogenation occurs in the vapor or liquid phase.
 5. The process ofclaim 2 wherein said hydrogenation is run in a batch mode or in acontinuous process.
 6. A process for the hydroformylation of alkenesinto their corresponding aldehydes or alcohols, said process comprisingcontacting an alkene containing from 2 to about 35 carbon atoms with asupported catalyst comprising a support, an anchoring agent, and a metalcomplex, wherein said anchoring agent is a heteropoly acid, its lacunaror other crystalline or non-crystalline phase or the respective anionand wherein said anchoring agent forms a bridge between the support andthe metal complex by direct interaction with the metal of said metalcomplex in the presence of H₂ and CO under conditions effective toconvert said alkene to a corresponding aldehyde and/or acid.
 7. Theprocess of claim 1 wherein said support is selected from the groupconsisting of metal oxides, carbon, resins and polymers.
 8. The processof claim 7 wherein the metal oxide is selected from the group consistingof alumina, silica, titania, lanthana, zeolites and clays.
 9. Theprocess of claim 7 wherein the support is a treated support.
 10. Theprocess of claim 9 wherein said treated support material is obtained bycalcining said support or contacting said support with a modifier. 11.The process of claim 10 wherein the modifier is a metal alkoxide. 12.The process of claim 11 wherein said metal alkoxide is titaniumalkoxide, aluminum alkoxide, silane alkoxide or vanadium alkoxide. 13.The process of claim 1 wherein said heteropoly acid is a Keggin type,Dawson type, Waugh type, Anderson type or Silverton type and said anionis an anion of the heteropoly acid.
 14. The process of claim 13 whereinthe Keggin type of said heteropoly acid is phosphotungstic acid,phosphomolybdic acid or silicotungstic acid or the anions thereof. 15.The process of claim 1 wherein the metal complex is a catalyticallyactive material which contains at least one metal atom or ion from GroupIIIB, IVB, VB, VIB, VIIB, VIII, IB or IIB of the Periodic Table ofElements to which one or more ligands are attached.
 16. The process ofclaim 15 wherein said metal atom or ion is from Group VIII of thePeriodic Table of Elements.
 17. The process of claim 15 wherein saidligand is selected from the group consisting of phosphines, amines,carbonyl, alkenes, dienes, halides, (R,R) or(S,S)2,2'-bis(diphenylphosphino)-1,1'-binapthyl(BINAP),(2S,3S)-bis(diphenylphosphino)butane (CHIRAPHOS), cyclooctadiene (COD),(R,R)-1,2-bis[(2 methoxyphenyl)phenylphosphine]ethane (DIPAMP),1,2-bis(2R,5R)-2,5(dimethylphospholano)benzene (Me-DUPHOS)(R)1,2-bis(diphenylphosphino)propane (PROPHOS),2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane(DIOP) and mixtures thereof.
 18. The process of claim 6 wherein saidsupport is selected from the group consisting of metal oxides, carbon,resins and polymers.
 19. The process of claim 18 wherein the metal oxideis selected from the group consisting of alumina, silica, titania,lanthana, zeolites and clays.
 20. The process of claim 6 wherein thesupport is a treated support.
 21. The process of claim 20 wherein saidtreated support material is obtained by calcining said support orcontacting said support with a modifier.
 22. The process of claim 21wherein the modifier is a metal alkoxide.
 23. The process of claim 22wherein said metal alkoxide is titanium alkoxide, aluminum alkoxide,silane alkoxide or vanadium alkoxide.
 24. The process of claim 6 whereinsaid heteropoly acid is a Keggin type , Dawson type, Waugh type,Anderson type or Silverton type and said anion is an anion of theheteropoly acid.
 25. The process of claim 24 wherein the Keggin type ofsaid heteropoly acid is phosphotungstic acid, phosphomolybdic acid orsilicotungstic acid or the anions thereof.
 26. The process of claim 6wherein the metal complex is a catalytically active material whichcontains at least one metal atom or ion from Group IIIB, IVB, VB, VIB,VIIB, VIII, IB or IIB of the Periodic Table of Elements to which one ormore ligands are attached.
 27. The process of claim 26 wherein saidmetal atom or ion is from Group VIII of the Periodic Table of Elements.28. The process of claim 26 wherein said ligand is selected from thegroup consisting of phosphines, amines, carbonyl, alkenes, dienes,halides, (R,R) or(S,S)2,2'-bis(diphenylphosphino)-1,1'-binapthyl(BINAP),(2S,3S)-bis(diphenylphosphino)butane (CHIRAPHOS), cyclooctadiene (COD),(R,R)-1,2-bis[(2 methoxyphenyl)phenylphosphine]ethane (DIPAMP),1,2-bis(2R,5R)-2,5(dimethylphopholano)benzene (Me-DUPHOS(R)1,2-bis(diphenylphosphino)propane (PROPHOS),2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane(DIOP) and mixtures thereof.
 29. A process for forming a C--X bond,wherein C is carbon and X is H, C, O, halogen, Si, alkoxy, or Ncomprising contacting an organic compound requiring formation of saidC--X bond with a support catalyst in the presence of a reactant underconditions capable of forming said C--X bond in said organic compound,wherein said supported catalyst comprises a support, an anchoring agent,and a metal complex, said anchoring agent is a heteropoly acid, itslacunar or other crystalline or non-crystalline or the respective anion,and said anchoring agent forms a bridge between the support and themetal complex by direct interaction with the metal of said metalcomplex.